Pattern forming material and pattern forming method

ABSTRACT

A pattern forming material according to an embodiment is a pattern forming material comprising a polymer composed of a plurality of monomer units bonded to each other. Each of the monomer units includes an ester structure having a first carbonyl group and at least one second carbonyl group bonded to the ester structure. A second carbonyl group farthest from a main chain of the polymer constituting the pattern forming material among second carbonyl groups is in a linear chain state.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is based upon and claims the benefit of priority. fromthe prior Japanese Patent Application No. 2018-005913, filed on Jan. 17,2018, the entire contents of which are incorporated herein by reference.

FIELD

The embodiments of the present invention relate to a pattern formingmaterial and a pattern forming method.

BACKGROUND

A technique to process a material into a pattern with a high aspectratio is demanded in a semiconductor manufacturing process. When amaterial is processed, a patterned mask is formed on the material andthe material is processed by dry etching using the mask. However, whenthe aspect ratio of the pattern of the material is high, the maskrequires a high resistance to etching because the mask is exposed to anetching gas for a long time.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A to 1C illustrate the stabilization energy ΔE when TMA isbrought close to PMMA or PS;

FIGS. 2A to 2C illustrate the stabilization energies ΔE when TMA isbrought close to PAcMA;

FIGS. 3A to 4B illustrate the stabilization energies ΔE when TMA isbrought close to PacacEMA having three carbonyl groups;

FIG. 5 is a table indicating the stabilization energies ΔE depending oncompositions of a side chain of a polymer;

FIG. 6 is a composition diagram illustrating an example of the patternforming material according to the present embodiment;

FIGS. 7A to 7E are composition diagrams illustrating examples of themonomer units constituting the polymer according to the presentembodiment;

FIG. 8 is a table indicating a relation between the combination ofmonomer units constituting the pattern forming material and the filmincrease rate obtained by metallization of the pattern forming materialaccording to the first embodiment;

FIG. 9 is a table indicating a relation between the combination ofmonomer units constituting a pattern forming material and the filmincrease rate obtained by metallization of the pattern forming materialaccording to a second embodiment; and

FIG. 10A to FIG. 11D are sectional views illustrating an example of apattern forming method according to a fourth embodiment.

DETAILED DESCRIPTION

Embodiments will now be explained with reference to the accompanyingdrawings. The present invention is not limited to the embodiments. Thedrawings are schematic or conceptual, and the ratios and the like amongrespective parts may not be the same as those of actual products. In thepresent specification and the drawings, elements identical to thosedescribed with respect to the foregoing drawings are denoted by likereference characters and detailed explanations thereof are omitted asappropriate.

A pattern forming material according to an embodiment is a patternforming material comprising a polymer composed of a plurality of monomerunits bonded to each other. Each of the monomer units includes an esterstructure having a first carbonyl group and at least one second carbonylgroup bonded to the ester structure. A second carbonyl group farthestfrom a main chain of the polymer constituting the pattern formingmaterial among second carbonyl groups is in a linear chain state.

(Pattern Forming Material)

When a processing target material is processed into a pattern with ahigh aspect ratio, a mask serving as a pattern forming material isexposed to an etching gas for a long time. Therefore, the maskpreferably has a high etching resistance.

A carbon film deposited by a CVD (Chemical Vapor Deposition) method isgenerally used as a mask. However, deposition of carbon by the CVDmethod takes a long time.

In contrast thereto, in the present embodiment, after a pattern formingmaterial is formed, the pattern forming material is impregnated withmetal and is bonded thereto. This metallizes the pattern formingmaterial and increases the etching resistance. Such a pattern formingmaterial can be formed in a shorter time than in the carbon depositionby the CVD method.

In order to further enhance the etching resistance, it is preferablethat a metallic compound is adsorbed to the pattern forming material ata high density. In order to enable a large quantity of a metalliccompound to be adsorbed, to which part of the pattern forming materialmetal adsorbs was verified. The result of the verification indicatedthat metal selectively adsorbed to carbonyl groups. That is, it is foundthat a metallic compound can be contained at a high density in thepattern forming material when the density of carbonyl groups in thepattern forming material is high.

The present embodiment is described below in more detail.

(Mechanism of Metallization)

When a metallic compound precursor (hereinafter, also simply“precursor”) to be used in a CVD method or an ALD (Atomic LayerDeposition) method is exposed to a polymer, a metallic compound isdeposited in the polymer. For example, when TMA (Trimethylaluminum)serving as a precursor is exposed to PMMA (Polymethylmethacrylate)serving as a polymer using an ALD apparatus, an aluminum oxide or ahydroxide is deposited in the PMMA. It is considered that the aluminumoxide or the hydroxide is formed because TMA approaches a carbonyl groupin PMMA and then electrostatic attraction is generated between aluminumand the carbonyl group.

In order to confirm that TMA approaches a carbonyl group and is bondedthereto, verification was performed based on a DFT (Density FunctionalTheory) using a molecular orbital calculation program.

A molecular structure was calculated using a molecular orbitalcalculation program (“Gaussian09” manufactured by HPC SYSTEMS Inc., forexample). A B3LYP (Becke, 3-parameter, Lee-Yang-Parr) method was used asa functional of the DFT. As a basis set for TMA and the polymer,6-31G(d) was used. When the precursor contained heavy metal, LanL2DZ wasused for the basis set for the precursor.

The stabilization energy of the precursor in a stabilized state istermed E1 and that the energy of the polymer in a stabilized state istermed E2. The energy in a state where the precursor is brought close toa segment at the center of the polymer from various directions followedby the precursor adsorbed to the polymer is termed E3. The overallstabilization energy is defined as ΔE, where ΔE=E1+E2-E3, the precursoris adsorbed to the polymer more stably when the stabilization energy ΔEhas a larger negative value.

FIGS. 1A to 1C illustrate the stabilization energy ΔE when TMA isbrought close to PMMA or PS (Polystyrene). In FIGS. 1A and 1B, PMMA isselected as a polymer. In FIG. 1C, PS is selected as a polymer. TMA isselected as a precursor in all FIGS. 1A to 1C.

When TMA is brought close to an oxygen atom of a carbonyl group at anester bond portion of PMMA as indicated by an arrow in FIG. 1A, TMA isattracted to the carbonyl group and is adsorbed thereto. Thestabilization energy ΔE was approximately −14.17 kcal/mol. The distancebetween the carbonyl group and Al was about 0.203 nanometer andsufficiently small. Accordingly, it was found out that TMA is adsorbedstably to the carbonyl group.

When TMA is brought close to an oxygen atom side bonded with a methylgroup at the ester bond portion of PMMA as indicated by an arrow in FIG.1B, TMA is dissociated and is not attracted. The stabilization energy ΔEwas approximately −3.71 kcal/mol.

When TMA is brought close to a benzene ring of PS as indicated by anarrow in FIG. 1C, TMA is dissociated and is not attracted. Thestabilization energy ΔE was approximately −2.66 kcal/mol. As describedabove, TMA is adsorbed to a polymer more stably as the stabilizationenergy ΔE has a larger negative value (ΔE is smaller) and thus it isknown that TMA is attracted to a carbonyl group having electron pairs.That is, by increasing the density of carbonyl groups in a polymer, thepolymer attracts TMA more stably and is metallized more easily.

TMA exists stably as a dimer rather than a monomer at a roomtemperature. When a monomer of TMA is transformed to a dimer, thestabilization energy ΔE becomes approximately −11.09 kcal/mol. On theother hand, when TMA is adsorbed to PMMA, the stabilization energy ΔEbecomes approximately −14.17 kcal/mol. Therefore, TMA is stabilized morein a state of being adsorbed to PMMA than in a state of being existingas a dimer. Accordingly, TMA is easily adsorbed to PMMA also at a roomtemperature. However, the difference (3.08 kcal/mol) is small and TMAhas a possibility of reverting to a dimer by a slight thermaldisturbance.

From the calculations described above, PMMA is preferable to PS as apolymer in a pattern forming material. However, TMA adsorbed into a PMMAfilm is a little more stabilized than a dimer of TMA. Therefore, whenthe concentration of TMA is increased, more TMA can be adsorbed stablyinto a PMMA film. When exposure to an oxidant such as H₂O is performedin a state where TMA is adsorbed into a PMMA film, the TMA adsorbed intothe PMMA film is oxidized. Accordingly, an aluminum oxide or a hydroxideis deposited in PMMA.

(Stabilization Energies ΔE of Various Polymers and TMA)

Comparing the stabilization energies ΔE of the various polymers and TMA,it was found that a polymer having a carbonyl group in a molecularstructure adsorbed TMA stably. It was also found that even having asimilar molecular structure to that of PMMA, PVA (Polyvinylacetate)having a different side chain had a larger stabilization energy ΔE (thatis, was more instable) than PMMA. Therefore, PMMA is more suitable as apolymer than PVA.

In order to enable TMA to be adsorbed stably to PMMA, it is preferablethat the distance between an oxygen atom of a carbonyl group of apolymer and an Al atom of the TMA fall in a range from about 0.20nanometer to 0.22 nanometer. It is considered that this is because TMAis stabilized due to the electron pairs of an oxygen atom. It isconsidered that adsorption of TMA to PMMA conversely becomes instablewhen the distance exceeds this range.

The stabilization energy ΔE has a positive correlation with a rate atwhich the film thickness changes when a polymer is metallized. That is,a polymer having a smaller stabilization energy ΔE (that is, being morestable) with TMA can adsorb more TMA in the polymer film and thus thefilm thickness is increased more when the polymer is metallized.Therefore, the change rate in the film thickness of a polymer before andafter metallization can be used as an index for the stabilization energyΔE.

(Various Precursors)

Adsorbing characteristics of precursors other than TMA are discussed.Possible precursors having a metallic element other than Al are TiCl₄,WCl₆, and VCl₄.

TiCl₄ was adsorbed to a carbonyl group of PMMA and the stabilizationenergy ΔE thereof was about −14.07 kcal/mol. There is TDMAT(Tetrakisdimethylaminotitanium) as a precursor for Ti. However, becausehaving a large molecular size, TDMAT cannot approach as a ligand to thevicinity of the carbonyl group of a polymer and is not stabilized.Therefore, it is considered that a precursor having a small molecularsize is advantageous.

WCl₆ was adsorbed to the carbonyl group and the stabilization energy ΔEwas about −10.13 kcal/mol.

VCl₄ was adsorbed to the carbonyl group and the stabilization energy ΔEwas about −14.47 kcal/mol.

From these results, also when TiCl₄, WCl₆, or VCl₄ is used as aprecursor other than TMA, such a precursor can be used similarly to TMAwhen the molecular size is small.

(Polymer Structure)

The above discussions show that increasing the density of carbonylgroups in a polymer facilitates stable metallization of the polymer.Therefore, it is preferable that more carbonyl groups are formed in amonomer unit (hereinafter, also “one segment”) of a polymer.Furthermore, it suffices that a precursor is adsorbed to a polymer tohave the stabilization energy ΔE with a larger negative value (smaller)than the stabilization energy between precursors. It is considered thatthis facilitates metallization of the polymer.

In the present embodiment, a polymer including a plurality of carbonylgroups in a monomer unit is therefore used as a pattern formingmaterial. For example, PAcMA (Polyacetonylmethacrylate) having twocarbonyl groups is used as a polymer.

FIGS. 2A to 2C illustrate the stabilization energies ΔE when TMA isbrought close to PAcMA. As illustrated in FIG. 2A, when TMA approaches acarbonyl group B1 located on a side close to a main chain of PAcMA, theTMA is attracted by the carbonyl group and adsorbs thereto. Thestabilization energy ΔE becomes about −12.55 kcal/mol.

As illustrated in FIG. 2B, when TMA approaches a carbonyl group B2located on a side far from the main chain of PAcMA, the TMA is attractedby the carbonyl group and adsorbs thereto. The stabilization energy ΔEbecomes about −15.99 kcal/mol. That is, TMA adsorbs stably to thecarbonyl group B2 on an outer side, which is less sterically hinderedthan the carbonyl group B1 on an inner side.

Furthermore, as illustrated in FIG. 2C, when two TMA are brought closeto PAcMA, the TMA adsorb to the carbonyl groups B1 and B2, respectively.The stabilization energy ΔE is about −25.89 kcal/mol. In this way, TMAhaving adsorbed to one of the carbonyl groups B1 and B2 does not inhibitTMA from adsorbing to the other of the carbonyl groups B1 and B2.

FIGS. 3A to 4B illustrate the stabilization energies ΔE when TMA isbrought close to PacacEMA (Poly (2-(acetoacetoxy)ethyl methacrylate)having three carbonyl groups. PacacEMA is a polymer having threecarbonyl groups B11 to B13.

As illustrated in FIG. 3A, when TMA approaches the carbonyl group B11located closest to a main chain of PacacEMA, the TMA is attracted by thecarbonyl group B11 and adsorbs thereto. The stabilization energy ΔE wasabout −14.53 kcal/mol.

As illustrated in FIG. 3B, when TMA approaches the carbonyl group B12located in the middle of PacacEMA, the TMA is attracted by the carbonylgroup B12 and adsorbs thereto. The stabilization energy ΔE was about−17.47 kcal/mol.

As illustrated in FIG. 3C, when TMA approaches the carbonyl group B13located at a farthest position from the main chain of PacacEMA, the TMAis attracted by the carbonyl group B13 and adsorbs thereto. Thestabilization energy ΔE was about −15.82 kcal/mol.

That is, TMA adsorbs most stably to the middle carbonyl group B12 amongthe carbonyl groups B11 to B13.

As illustrated in FIG. 4A, when two TMA approach PacacEMA, the TMAadsorb to the two carbonyl groups B12 and B13 on an outer side,respectively. The stabilization energy ΔE was about −30.84 kcal/mol.

As illustrated in FIG. 4B, when three TMA approach PacacEMA, the TMAadsorb to the three carbonyl groups B11 to B13, respectively. Thestabilization energy ΔE was about −43.81 kcal/mol.

As described above, it was found that three TMA could adsorb to PacacEMAstably even when three TMA approached PacacEMA at the same time. In thepresent embodiment, metallization of a polymer using the molecularorbital method was simulated.

(Linear Chain and Alicyclic Compound)

FIG. 5 is a table indicating the stabilization energies ΔE depending oncompositions of a side chain of a polymer. This table indicates that TMAis stable when being adsorbed to a carbonyl group of a polymer locatedon an outermost side (a distal end) among a plurality of carbonyl groupsthereof regardless of whether the side chain is a linear chain or analiphatic cyclic compound (an alicyclic compound). This table alsoindicates that the stabilization energy ΔE is larger as TMA is adsorbedto a carbonyl group located on an inner side. That is, TMA is adsorbedto a carbonyl group located on an outer side of the side chain first.This shows that absorption of TMA to a carbonyl group located at thedistal end of the side chain is important.

A comparison between a case where the side chain of a polymer is alinear chain and a case where the side chain is an alicyclic compoundshows that the linear chain is more stable than the alicyclic compound.For example, when TMA was adsorbed to the carbonyl group B3 at thedistal end of a linear chain, the stabilization energy ΔE was about−19.56 kcal/mol. When TMA was adsorbed to the carbonyl group B3 at thedistal end of an alicyclic compound, the stabilization energy ΔE wasabout −17.90 kcal/mol. This is because when there is an alicycliccompound in the side chain of a polymer, the alicyclic compound becomesa steric hinderance and causes difficulty in adsorption of TMA. Asdescribed above, a polymer in which the side chain is a linear chain ismore easily metallized with TMA and is more advantageous than a polymerin which the side chain is an alicyclic compound even when thesepolymers have similar molecular structures.

From the above discussions, it is found that the pattern formingmaterial is preferably a polymer having a high density of carbonylgroups and including no alicyclic compound in the side chain.

FIG. 6 is a composition diagram illustrating an example of the patternforming material according to the present embodiment. A polymer 1illustrated in FIG. 6 is a polymer composed of a plurality of monomerunits (monomers) 10 bonded to each other. The polymer 1 in FIG. 6 is,for example, PAcMA (Polyacetonylmethacrylate). In FIG. 6, n is apositive number equal to or larger than 2.

The monomer units 10 each include an ester structure 20 having a firstcarbonyl group 30_1, and at least one second carbonyl group 30_2.

The main chain of the polymer 1 can be formed of a plurality of theester structures 20 sequentially bonded to each other. Me indicates amethyl group and the ester structure 20 is included in a methacrylicester structure in this case.

The polymer 1 according to the present embodiment further includes thesecond carbonyl group 30_2 bonded to the first carbonyl group 30_1. Thesecond carbonyl group 30_2 is bonded as a side chain to the main chain.

The distal end of the side chain has a methyl group connected to thesecond carbonyl group 30_2. The second carbonyl group 30_2 farthest fromthe ester structure 20 is not included in a cyclic structure such as abenzene ring or an alicyclic compound. That is, the side chain does nothave a cyclic structure and is a linear chain.

As described above, the monomer unit 10 of the polymer 1 according tothe present embodiment has the plural carbonyl groups 30_1 and 30_2.Furthermore, there is no cyclic structure such as a benzene ring or analicyclic compound at the distal end of the side chain of the monomerunit 10. Therefore, the density of carbonyl groups included in thepolymer 1 is high and the polymer 1 can adsorb more metallic precursors(TMA, for example). Furthermore, the polymer 1 can be metallized stably.For example, because the second carbonyl group 30_2 farthest from themain chain is in the form of a linear chain and is less stericallyhindered, metal can be more easily adsorbed also to the first carbonylgroup 30_1 in the ester structure 20.

Monomer units of a polymer having identical characteristics can be, forexample, a monomer containing at least one of (meth)acrylic aceticanhydride illustrated in FIG. 7A, acetonyl (meth)acrylate illustrated inFIG. 7B, (meth)acrylic acid-3-oxobutanoic anhydride illustrated in FIG.7C, (meth)acrylic acid-2,4-dioxopentyl ester illustrated in FIG. 7D, and2-(acetoacetoxy)ethyl (meth)acrylate illustrated in FIG. 7E. Each of themonomer units will be explained later with reference to FIGS. 7A to 7E.

The polymer according to the present embodiment can be a homopolymercomposed of one type of the monomers described above as the monomerunits 10. The polymer according to the present embodiment canalternatively be a copolymer composed of at least one type of themonomers described above as the monomer units 10. Furthermore, thepolymer can be a polymer blend material being a blend of plural types ofhomopolymers each composed of one type of the monomers described aboveas the monomer units 10.

FIGS. 7A to 7E are composition diagrams illustrating examples of themonomer units constituting the polymer 1 according to the presentembodiment.

FIG. 7A illustrates a monomer unit M1 having two carbonyl groups. When Ris hydrogen (H), the monomer unit M1, is acrylic acetic anhydride. WhenR is a methyl group (CH₃), the monomer unit M1 is methacrylic aceticanhydride.

FIG. 7B illustrates a monomer unit M2 having two carbonyl groups. When Ris hydrogen (H), the monomer unit M2 is acetonyl acrylate. When R is amethyl group (CH₃), the monomer unit M2 is acetonyl methacrylate.

FIG. 7C illustrates a monomer unit M3 having three carbonyl groups. WhenR is hydrogen (H), the monomer unit M3 is acrylic acid-3-oxobutanoicanhydride. When R is a methyl group (CH₃), the monomer unit M3 ismethacrylic acid-3-oxobutanoic anhydride.

FIG. 7D illustrates a monomer unit M4 having three carbonyl groups. WhenR is hydrogen (H), the monomer unit M4 is acrylic acid-2,4-dioxopentylester. When R is a methyl group (CH₃), the monomer unit M4 ismethacrylic acid-2,4-dioxopenthyl ester.

FIG. 7E illustrates a monomer unit M5 having three carbonyl groups. WhenR is hydrogen (H), the monomer unit M5 is 2-(acetoacetoxy)ethylacrylate. When R is a methyl group (CH₃), the monomer unit M5 is2-(acetoacetoxy)ethyl methacrylate.

The monomer units constituting the polymer 1 according to the presentembodiment can be the monomer illustrated in any of FIGS. 7A to 7E.

The monomer units M3 to M5 are subjected to appropriate treatment in thepolymer 1 to be insolubilized in a solvent. Accordingly, even when anSOG (Spin-On Glass) film or the like is coated on the pattern formingmaterial containing an identical solvent, the pattern forming materialdoes not dissolve and can maintain the shape.

The (acetoacetoxy)ethyl (meth)acrylate can also be insolubilizedsimilarly.

The polymer 1 of the pattern forming material can be a copolymer being acombination of plural types of monomers. By adjusting the combination ofplural types of monomers, it is possible to adjust characteristics of acopolymer, such as solubility in a solvent, a film forming property atthe time of being coated, and a glass transition temperature of a filmafter coated. Examples of a copolymer being a combination of pluraltypes of monomers are copolymers obtained by adding styrene,hydroxystyrene, (meth)acrylic acid methyl, (meth)acrylic acid ethyl, or(meth)acrylic acid hydroxylethyl to the monomer according to the presentembodiment.

On the other hand, a copolymer obtained by adding a monomer including nocarbonyl group to the monomer according to the present embodimentadversely reduces the density of carbonyl groups. Accordingly, it ispreferable that the ratio of monomers including no carbonyl groups issuppressed to be lower than about 50 mol %.

The polymer 1 of the pattern forming material can alternatively be acopolymer or a polymer blend obtained by adding a monomer including nocarbonyl group to any of the monomer units M3 to M5. This also caninsolubilize the pattern forming material in a solvent.

A solvent that dissolves the polymer 1 according to the presentembodiment to form a solution is not particularly limited. The solventcan be, for example, any of 1-butanol, N,N-dimethylformamide,N-methylpyrrolidone, γ-butyrolactone, acetone, anisole, isobutylalcohol, isopropyl alcohol, isopentyl alcohol, ethylene glycol monoethylether, ethylene glycol monoethyl ether acetate, ethylene glycolmono-n-butyl ether, ethylene glycol monomethyl ether, ethylene glycolmonomethyl ether acetate, xylene, cresol, cyclohexanol, cyclohexanone,tetrahydrofuran, toluene, ethyl lactate, propylene glycol monoethylether, propylene glycol monoethyl ether acetate, propylene glycolmono-n-butyl ether, propylene glycol monomethyl ether, propylene glycolmonomethyl ether acetate, methyl ethyl ketone, methyl cyclohexanol,methyl cyclohexanone, methyl-n-butyl ketone, isobutyl acetate, isopropylacetate, isopentyl acetate, ethyl acetate, n-butyl acetate, n-propylacetate, or n-pentyl acetate.

Relation Between Polymer Film Thickness and Metallization: ReferenceExample

A reference example is explained first. In the reference example, PMMAhaving one carbonyl group is used as a polymer. A polymer solution isproduced by dissolving 0.1 gram of PMMA illustrated in FIGS. 1A to 1C in9.9 grams of propylene glycol monomethyl ether acetate. As illustratedin FIGS. 1A to 1C, PMMA has only one carbonyl group in the monomer unit.This polymer solution is spin-coated as a pattern forming material ontoa silicon substrate. The film thickness of the pattern forming materialis, for example, about 50 nanometers.

Next, the silicon substrate is placed in a vacuum chamber and is exposedto a TMA atmosphere. Accordingly, TMA is penetrated into the patternforming material.

Subsequently, the silicon substrate is exposed to water vapor to oxidizeTMA in the pattern forming material. When the film thickness of thepattern forming material was measured after vacuum drying, the filmthickness was about 55 nanometers. That is, when PMMA was selected asthe pattern forming material, the film increase rate of the patternforming material after metallization was about 10%.

Relation Between Polymer Film Thickness and Metallization: FirstEmbodiment

In contrast, a homopolymer or a copolymer illustrated in FIG. 8 is usedas a pattern forming material according to a first embodiment. FIG. 8 isa table indicating a relation between the combination of monomer unitsconstituting the pattern forming material and the film increase rateobtained by metallization of the pattern forming material according tothe first embodiment.

First and second monomer units are any of monomers M1-H, M1-Me, M2-H,M2-Me, M3-1-1, M3-Me, M4-H, M4-Me, M5-H, and M5-Me. The monomers M1-H,M2-H, M3-H, M4-H, and M5-H are the monomers illustrated in FIG. 7 andare acrylic ester monomers. The monomers M1-Me, M2-Me, M3-Me, M4-Me, andM5-Me are the monomers illustrated in FIG. 7 and are methacrylic estermonomers.

In FIG. 8, for example, when the first and second monomer units are boththe monomer M1-H, the pattern forming material becomes a homopolymer ofM1-H. Similarly, when the first and second monomer units are both a samemonomer (any of M2-H to M5-H and M1-Me to M5-Me), the pattern formingmaterial becomes a homopolymer of that monomer.

For example, when the first monomer unit is the monomer M1-H and thesecond monomer unit is the monomer M1-Me, the pattern forming materialbecomes a copolymer of M1-H and M1-Me. Similarly, when the first andsecond monomer units are monomers different from each other, the patternforming material becomes a copolymer including the first and secondmonomer units.

Synthesis of a homopolymer or a copolymer was performed in a mannerdescribed below. A total amount of 1 millimole of the first and secondmonomer units and 0.01 millimole of azobisisobutyronitrile were reactedwith each other for 8 hours in 50 milliliters of THF (Tetrahydrofuran)in a nitrogen atmosphere at 60° C. After reprecipitation in methanol,and dried in vacuum a homopolymer or a copolymer was obtained.

The pattern forming material was produced by dissolving 0.1 gram of thehomopolymer or copolymer in 9.9 grams of propylene glycol monomethylether acetate. This pattern forming material was spin-coated onto asilicon substrate and was annealed for 10 minutes at 160° C. to obtain athin film with a thickness of 50 nanometers.

Thereafter, the pattern forming material was metallized with TMA in thesame manner as in the reference example, and the film increase rate wascalculated.

In the table illustrated in FIG. 8, all the homopolymers or thecopolymers obtained by combining the first and second monomer units havethe film increase rate of about 20 to 50% after metallization. That is,it was found that the film thickness of the pattern forming materialaccording to the present embodiment was increased by about 20 to 50% bythe metallization due to TMA.

Compared to the film increase rate (10%) of PMMA in the referenceexample, the film increase rate of the pattern forming materialaccording to the present embodiment is larger. This indicates that thepattern forming material according to the first embodiment can adsorbmore metal than PMMA.

Relation Between Polymer Film Thickness and Metallization: SecondEmbodiment

FIG. 9 is a table indicating a relation between the combination ofmonomer units constituting a pattern forming material and the filmincrease rate obtained by metallization of the pattern forming materialaccording to a second embodiment. The first monomer units according tothe second embodiment are the same as those in the first embodiment.However, the second monomer units according to the second embodiment arematerials different from the second monomer units according to the firstembodiment.

The second monomer unit is any of St (Styrene), St-OH (Hydroxystyrene),MMA (Methyl methacrylate), MAA (Methyl acrylate), EMA (Ethylmethacrylate), EAA (Ethyl acrylate), HEMA (Hydroxylethyl methacrylate),and HEAA (Hydroxyl ethyl acrylate).

In the second embodiment, for example, when the first monomer unit isthe monomer M1-H and the second monomer unit is St (Styrene), thepattern forming material becomes a copolymer of M1-H and St. Similarly,the pattern forming material becomes a copolymer of the first and secondmonomer units.

Synthesis of a copolymer can be performed in the same manner as that ofthe polymer described in the first embodiment. The pattern formingmaterial also can be produced by the same method as that describedabove. Thereafter, the pattern forming material was metallized with TMAand the film increase rate was calculated in the same manner as that inthe first embodiment.

In the table illustrated in FIG. 9, all the copolymers formed bycombining the first and second monomer units have the film increase rateof about 10 to 30% after metallization.

Compared to the film increase rate (10%) of PMMA in the referenceexample, all the copolymers illustrated in FIG. 9 are larger in the filmincrease rate of the pattern forming material. This indicates that thepattern forming material according to the second embodiment can adsorbmore metal than PMMA.

Relation Between Polymer Film Thickness and Metallization: ThirdEmbodiment

In a third embodiment, the solvent used for the pattern forming materialis changed. For example, a pattern forming material was produced bydissolving 0.1 gram of poly acetonyl acrylate in 9.9 grams of a solvent.The solvent used at this time is 1-butanol, N,N-dimethylformamide,N-methylpyrrolidone, γ-butyrolactone, acetone, anisole, isobutylalcohol, isopropyl alcohol, isopentyl alcohol, ethylene glycol monoethylether, ethylene glycol monoethyl ether acetate, ethylene glycolmono-n-butyl ether, ethylene glycol monomethyl ether, ethylene glycolmonomethyl ether acetate, xylene, cresol, cyclohexanol, cyclohexanone,tetrahydrofuran, toluene, ethyl lactate, propylene glycol monoethylether, propylene glycol monoethyl ether acetate, propylene glycolmono-n-butyl ether, propylene glycol monomethyl ether, propylene glycolmonomethyl ether acetate, methyl ethyl ketone, methyl cyclohexanol,methyl cyclohexanone, methyl-n-butyl ketone, isobutyl acetate, isopropylacetate, isopentyl acetate, ethyl acetate, n-butyl acetate, n-propylacetate, or n-pentyl acetate.

The pattern forming material was metallized with TMA and the filmincrease rate was calculated in the same manner as that in the firstembodiment. As a result, with use of any of the solvents, the filmthickness of the pattern forming material was increased by about 50%after metallization. Therefore, it was found that the effect of thepresent embodiment was not lost with use of any of the solventsdescribed above.

(Pattern Forming Method)

A pattern forming method according to the present embodiment isexplained next.

FIG. 10A to FIG. 11D are sectional views illustrating an example of apattern forming method according to a fourth embodiment. Any of thepolymers and the solvents in the first to third embodiments describedabove can be used for a pattern forming material used in the patternforming method according to the fourth embodiment.

First, a stack body 50 is deposited on a semiconductor substrate 40 asillustrated in FIG. 10A. The semiconductor substrate 40 can be glass,silicon, quartz, mica, or the like. The stack body 50 is, for example, astack body formed by alternately stacking silicon nitride films andsilicon oxide films using the CVD method or the ALD method. The stackbody 50 can be, for example, a stack body to be used when a solid memorycell array of a NAND EEPROM (Electrically Erasable ProgrammableRead-Only Memory) is manufactured. In the fourth embodiment, the stackbody 50 being a processing target material is processed into a patternwith a high aspect ratio.

After the stack body 50 is formed, a pattern forming material 60 iscoated on the stack body 50 as illustrated in FIG. 10B. The formingmethod of the pattern forming material 60 can be, for example, a spincoating method, a dip coating method, a bar coating method, or vapordeposition. More specifically, the pattern forming material 60 isproduced by dissolving about 0.1 gram of the polymer 1 in 9.9 grams ofpropylene glycol monomethyl ether acetate. This pattern forming material60 is spin-coated on the stack body 50. The semiconductor substrate 40is annealed for 10 minutes in an atmosphere at about 160° C. to form thepattern forming material 60 with a thickness of 50 nanometers on thestack body 50. This annealing treatment can remove the solvent ormoisture in the pattern forming material 60 or can insolubilize thepattern forming material 60 in the solvent. Insolubilizing the patternforming material 60 in the solvent enables the pattern forming material60 to be insolubilized in the same solvent for the pattern formingmaterial 60 or a solvent for SOG.

The annealing temperature of the pattern forming material 60 ispreferably equal to or higher than about 120° C. to remove moisture. Inorder to remove moisture more reliably, it is more preferable that theannealing temperature is equal to or higher than about 150° C. On theother hand, if heated at a temperature exceeding 400° C., the patternforming material 60 is decomposed. Therefore, the pattern formingmaterial 60 is heated preferably at a temperature lower than about 400°C., more preferably at a temperature lower than 300° C. Before thepattern forming material 60 is formed, the stack body 50 can bepretreated. The pretreatment can be, for example, plasma treatment,ultraviolet irradiation treatment, or exposure treatment to an acid orozone.

Next, an antireflective film 65 is deposited on the pattern formingmaterial 60 as illustrated in FIG. 10C. For example, for light exposurewith a wavelength of 193 nanometers of ArF laser, resin containing abenzene ring is used as the antireflective film 65, and a material suchas novolac resin, phenol resin, or polyhydroxystyrene is used.

Subsequently, as illustrated in FIG. 10C, a SOG film 70 is coated on theantireflective film 65 and is heated for about 10 minutes in anatmosphere at about 230° C. to solidify the SOG film 70. The SOG film 70can be replaced by a SOC (Spin-On Carbon) film.

Next, as illustrated in FIG. 11A, a resist film 80 is coated on the SOGfilm 70 using a lithography technique and the resist film 80 ispatterned. The resist film 80 is patterned into a processing pattern ofthe stack body 50. For example, the resist film 80 is patterned into aplurality of hole patterns with a diameter of about 60 nanometers. Thepitch between adjacent ones of the hole patterns is about 100nanometers.

Next, the SOG film 70, the antireflective film 65, and the patternforming material 60 are processed using the resist film 80 as a mask asillustrated in FIG. 11B. For example, the SOG film 70, theantireflective film 65, and the pattern forming material 60 areprocessed by a RIE (Reactive Ion Etching) method or a CDE (Chemical DryEtching) method.

Accordingly, the patterns of the resist film 80 are transferred onto theSOG film 70, the antireflective film 65, and the pattern formingmaterial 60.

Subsequently, after the SOG film 70 and the antireflective film 65 areremoved, the semiconductor substrate 40 is placed in a vacuum chamberand is exposed for 10 minutes to gas or liquid of TMA at a temperaturebetween 50° C. and 200° C. to bind TMA to the pattern forming material60. If the gas or liquid has a temperature lower than 50° C., immersionof TMA becomes instable due to fluctuation of external air. On the otherhand, if the temperature is equal to or higher than 200° C., TMA isdifficult to adsorb to the pattern forming material 60. Next, thesemiconductor substrate 40 is exposed to a water vapor atmosphere for 10minutes to oxidize TMA in the pattern forming material 60. Accordingly,the pattern forming material 60 is metallized as illustrated in FIG.11C.

After the semiconductor substrate 40 is dried in a vacuum, the stackbody 50 is processed using the pattern forming material 60 as a mask.For example, the stack body 50 is processed by the RIE method or the CDEmethod using a CF₄ gas. Accordingly, the stack body 50 is processed intothe hole patterns described above as illustrated in FIG. 11D. Thepattern forming material 60 becomes a mask containing a relatively largeamount of metal, having a high etching resistance, and being solid.Therefore, when the pattern forming material 60 is used as a mask, apattern with a high aspect ratio can be easily formed on the stack body50.

Thereafter, a memory cell array is formed by a known method. Forexample, when the hole patterns formed on the stack body 50 are used asmemory holes, a block film, a charge accumulation layer, a gatedielectric film, and a silicon body are formed (not illustrated) as amemory structure in the memory holes. One (the silicon nitride film, forexample) of the insulating films of the stack body 50 is then replacedby a conductive material such as polysilicon or metal that functions asword lines WL. The silicon body functions as a channel. The chargeaccumulation layer functions as a data storage layer that accumulatestherein charges injected from the silicon body via the gate dielectricfilm. The block film suppresses the charges accumulated in the chargeaccumulation layer from diffusing to the word lines WL. In this way, thepattern forming material 60 can be used for formation of memory holes ina memory cell array, or the like.

In the fourth embodiment, the processing target material is the stackbody 50. However, the processing target material is not particularlylimited and can be the semiconductor substrate 40 or any other materiallayers. For example, the processing target material can be a singlelayer of the silicon dioxide films or the silicon nitride films. Theprocessing target material can alternatively be a metal layer or ametallic compound layer to be used as a hard mask material. The metallayer or the metallic compound layer can be, for example, any of W, Ta,Mo, Al, Ti, Zr, and Hf. The processing target material can be a layerincluding a plurality of materials as the stack body 50.

(Notes)

A cyclic structure does not need to be bonded to the second carbonylgroup farthest from the main chain of the polymer constituting thepattern forming material.

The pattern forming method according to the present embodiment canfurther includes, after coating the pattern forming material on theprocessing target material, forming a SOG film on the pattern formingmaterial, and forming an antireflective film on the SOG film.

The metallic precursor can be any of TMA, TiCl₄, WCl₆, and VCl₄.

The monomer unit can include at least one of (meth)acrylic aceticanhydride, acetonyl (meth)acrylate, (meth)acrylic acid-3-oxobutanoicanhydride, (meth)acrylic acid-2,4-dioxopentyl ester, and2-(acetoacetoxy)ethyl methacrylate.

The copolymer can include a copolymer of the monomer unit and any ofstyrene, hydroxystyrene, methyl (meth)acrylate, ethyl (meth)acrylate,and hydroxyethyl (meth)acrylate.

The solvent that dissolves the monomer unit can be any of 1-butanol,N,N-dimethylformamide, N-methylpyrrolidone, γ-butyrolactone, acetone,anisole, isobutyl alcohol, isopropyl alcohol, isopentyl alcohol,ethylene glycol monoethyl ether, ethylene glycol monoethyl etheracetate, ethylene glycol mono-n-butyl ether, ethylene glycol monomethylether, ethylene glycol monomethyl ether acetate, xylene, cresol,cyclohexanol, cyclohexanone, tetrahydrofuran, toluene, ethyl lactate,propylene glycol monoethyl ether, propylene glycol monoethyl etheracetate, propylene glycol mono-n-butyl ether, propylene glycolmonomethyl ether, propylene glycol monomethyl ether acetate, methylethyl ketone, methyl cyclohexanol, methyl cyclohexanone, methyl-n-butylketone, isobutyl acetate, isopropyl acetate, isopentyl acetate, ethylacetate, n-butyl acetate, n-propyl acetate, or n-pentyl acetate.

While certain embodiments have been described, these embodiments havebeen presented by way of example only, and are not intended to limit thescope of the inventions. Indeed, the novel methods and systems describedherein may be embodied in a variety of other forms; furthermore, variousomissions, substitutions and changes in the form of the methods andsystems described herein may be made without departing from the spiritof the inventions. The accompanying claims and their equivalents areintended to cover such forms or modifications as would fall within thescope and spirit of the inventions.

1. A pattern forming material comprising a polymer composed of aplurality of monomer units bonded to each other, wherein each of themonomer units includes: an ester structure having a first carbonylgroup; and at least one second carbonyl group bonded to the esterstructure, wherein a second carbonyl group among second carbonyl groups,which is farthest from a main chain of the polymer constituting thepattern forming material, is in a linear chain state, the monomer unitsinclude at least one of (meth)acrylic acetic anhydride, acetonyl(meth)acrylate, (meth)acrylic acid-3-oxobutanoic anhydride,(meth)acrylic acid-2,4-dioxopentyl ester, and 2-(acetoacetoxy)ethyl(meth)acrylate, and the polymer includes a homopolymer of the monomerunits or a copolymer including the monomer units equal to or higher than50 mol %. 2-4. (canceled)
 5. The material of claim 1, wherein thecopolymer includes a copolymer of the monomer unit and any of styrene,hydroxystyrene, methyl (meth)acrylate, ethyl (meth)acrylate, and hydroxyethyl (meth)acrylate.
 6. (canceled)
 7. The material of claim 1, furthercomprising a solvent dissolving the polymer, wherein the solvent is anyof 1-butanol, N,N-dimethylformamide, N-methylpyrrolidone,γ-butyrolactone, acetone, anisole, isobutyl alcohol, isopropyl alcohol,isopentyl alcohol, ethylene glycol monoethyl ether, ethylene glycolmonoethyl ether acetate, ethylene glycol mono-n-butyl ether, ethyleneglycol monomethyl ether, ethylene glycol monomethyl ether acetate,xylene, cresol, cyclohexanol, cyclohexanone, tetrahydrofuran, toluene,ethyl lactate, propylene glycol monoethyl ether, propylene glycolmonoethyl ether acetate, propylene glycol mono-n-butyl ether, propyleneglycol monomethyl ether, propylene glycol monomethyl ether acetate,methyl ethyl ketone, methyl cyclohexanol, methyl cyclohexanone,methyl-n-butyl ketone, isobutyl acetate, isopropyl acetate, isopentylacetate, ethyl acetate, n-butyl acetate, n-propyl acetate, or n-pentylacetate. 8-15. (canceled)